Synthetic leather

ABSTRACT

Synthetic leather-like coating composition containing a major amount of polyglutamic acid- gamma -ester and a minor amount of an acidic amino acid derivative. The amino acid derivative is alkyl or aralkyl or acyl esters such as, for example amino maleic acid, aspartic acid, glutamic acid, Alpha -aminosuberic, Alpha -aminosebacic acid, Beta -methylaspartic acid, Beta hydroxyaspartic acid, Beta -alkoxyaspartic acid, Beta hydroxygulatmic acid, Beta -alkoxyglutamic acid, 2-pyrrolidone5-carboxylic acid and the like, and the alkyl or aralkyl or acyl esters of N,N-dialkyl compounds of said acidic amino acids. The composition is coated on or impregnated into a cloth substrate.

United States Patent [191 Fujimoto et a1.

[ March 6, 1973 SYNTHETIC LEATHER [73] Assignee: Kyowa Hakko Kogyo Co.,Ltd.,

Tokyo, Japan [22] Filed: Nov. 13, 1970 [21] Appl. No.: 89,466

Related US. Application Data [62] Division of Ser. No. 761,853, Sept.23, 1968, abandoned.

[30] Foreign Application Priority Data Oct. 20, 1967 Japan ..43/67192June 4, 1968 Japan ..44/37769 [52] U.S.Cl ..1l7/76 T, 117/76 F, 117/126GB,

l17/138.8 A, 117/139, 117/141, ll7/l42,

UN, 117/164, 260/78 A [51] Int. Cl. ..D06n 3/04, D06n 3/12 [58] Field ofSearch ....1 17/76 T, 72 F, 164, 138.8 A, 1l7/l61 UA, 161 UN; 260/78 A[56] References Cited UNITED STATES PATENTS 3,537,871 11/1970 Kaneko..117l76 T X 3,582,442 6/1971 Kaneko ..1 17/76 T X 3,582,397 6/1971Shibata ..117/138.8 N 3,369,026 2/1968 lwatsuki et al.... ..260/78 A X3,230,274 1/1966 Garber et al ..260/78 A X Primary Examiner-Ralph HusackAttorney-Craig, Antoneili & Hill [5 7] ABSTRACT Synthetic leather-likecoating composition containing a major amount of polyglutamicacid-'y-ester and a minor amount of an acidic amino acid derivative. Theamino acid derivative is alkyl or aralkyl or acyl esters such as, forexample amino maleic acid, aspartic acid, glutamic acid, a-aminosuberic,a-aminosebacic acid, B-methylaspartic acid, B-hydroxyaspartic acid,B-alkoxyaspartic acid, B-hydroxygulatmic acid, B-alkoxyglutamic acid,2-pyrroiidone-5-carboxy1ic acid and the like, and the alkyl or aralkylor acyl esters of N,N- dialkyl compounds of said acidic amino acids. Thecomposition is coated on or impregnated into a cloth substrate.

6 Claims, No Drawings SYNTHETIC LEATHER This is a divisional ofapplication Ser. No. 761,853, filed Sept. 23, 1968, now abandoned.

The present invention relates to a process for producing an improvedsynthetic leather in which polymer (homoor copolymer or blend polymer)of glutamic acid-y-ester or esters with or without other amino acids isused as the main constituent thereof. More particularly, the presentinvention is directed to an improved synthetic leather which exhibitssubstantially the same properties of, for example, tensile strength,elongation, etc., as those of natural leather.

As the conventional synthetic leather-like materials, it is well knownto use such materials as so called polyvinyl chloride leather, polyamideleather, polyurethane leather, and the like. These materials areprepared by respectively treating the substrate cloth with polyvinylchloride, a polyamide, a polyurethane, and the like. However, thesematerials respectively have various defects when compared with naturalleathers. Recently, polyamino acid leather having the propertiesresembling natural leathers in quality has also been developed. Thispolyamino acid leather is prepared according to the same process as inthe production of the conventional synthetic leathers, wherein naturalfibers, synthetic fibers, unwoven (nonwoven) fabrics or synthetic resinsheets are coated with film of polymer (homoor co-polymer or blendpolymer) of glutamic acid-'y-ester or esters with or without other aminoacids (hereinafter referred to merely as polyglutamic acid-y-ester)formed thereon. The properties of synthetic leather thus obtained aremainly dominated by the properties of polyglutamic acid-'y-ester filmformed on the surface thereof, though such properties of syntheticleather are often influenced by the kind of substrate cloths ormaterials employed. Comparing the properties of polyglutamicacid-y-ester films with those of the silver surface of natural leather,there are substantial differences between the two in tensile strengthand elongation, as shown in Table 1. Because of these differences, thepolyamino acid leather cannot sufficiently provide the feeling,touching, appearance, body, substance and characteristics of naturalleather.

TABLE 1 Comparison of Silver Surface of Natural Leather With Film ofPolyglutamic Acid-'y-methylester Silver surface Film of polyof naturalglutamic acidleather -y-methylester Tensile strength 120 300 Elongation140 40 (Rate of tension: 200 mm/min., tension test at 26C.)

Extensive studies have been made to find a method for making filmshaving properties closely resembling those of natural leathers, therebyovercoming the above-mentioned drawbacks.

An object of the present invention is to avoid the prior artdisadvantages in producing synthetic leathers.

Another object of the present invention is to provide an improvedsynthetic leather which contains many of the properties of naturalleather, such as for example, a similar tensile strength and elongation.

A further object of the present invention is to provide an improvedsynthetic leather which very closely resembles natural leather inpossessing such properties as an improved antistatic power, a reductionin dust adsorption, and the like.

Still another object of the present invention is to provide an improvedsynthetic leather wherein a substrate is coated with a film to produce aproduct which is leather-like in nature.

Other objects and further scope of applicability of the presentinvention will become apparent from the detailed description givenhereinafter; it should be understood, however, that the detaileddescription and specific examples, while indicating preferredembodiments of the invention, are given by way of illustration only,since various changes and modifications within the spirit and scope ofthe invention will become apparent to those skilled in the art from thisdetailed description.

Pursuant to the present invention, it has been found that theabove-mentioned disadvantages may be eliminated and a much improved filmhaving properties which more closely resemble those of the silversurface of natural leather can be obtained by preparing films from amaterial obtained by adding acidic amino acid derivative to polyglutamicacid-y-esters. An illustration demonstrating an embodiment of the abovefinding is shown in Table 2.

TABLE 2 Properties of Film Obtained From a Mixture of Poly-7-methylglutamate and Dibutyl Glutamate Ester Amount of dibutyl glutamateester based on the content of the polymer to be mixed (Rate of tension:200 mmlmin., tension test at 26C.)

It has been found that a synthetic leather prepared by forming this filmon a cloth substrate shows improved properties which more closelyresemble those of natural leather. Furthermore, a surprising fact foundby the present inventors was the phenomenon that intrinsic volumeresistivity of said film markedly decreases by the addition thereto ofan acidic amino acid derivative, which has resulted in the presentinvention.

For example, poly-'y-methyl-L-glutamic acid film showed an intrinsicvolume resistivity (voltage: V) of 4.86 X 10" Gem, whereas that of thefilm obtained from poly-'y-methyl-L-glutamic acid to which 10 percent ofdibutyl glutamate ester has been added was found to be a value less than10'. The above fact is considered to be ascribable to the synergisticaction between said diester and polyglutamic acid-'y-ester simultaneouswith the effect being obtained by the addition thereto of said diester.When the polyglutamic acid-y-esters in which the acidic amino acidderivative has been added is used as films in the production ofsynthetic leathers, as mentioned above, they exhibit substantiallyimproved properties due to the newly imparted antistatic power togetherwith the aforesaid physical properties, whereby its adsorption of dustand the like from the air is substantially reduced.

Sheet-like articles good in quality can be obtained by impregnating orcoating the substrates with an organic solvent solution prepared bythoroughly kneading an organic solvent solution of polyglutamicacid-'y-esters with an acidic amino acid derivative (or its organicsolvent solution) and then air-drying, drying under heating, orcoagulating the polymer by dipping the resultant product into acoagulating liquid containing water,

lower alcohols, ketones, hydrocarbons or a mixture thereof. Of course,it is also possible that a known adhesive can be interposed between thesubstrate and a film formed by a mixture of polyglutamic acid ester andan acidic acid derivative to strengthen the adhesion thereof to thesubstrate.

As the substrate, there may be used a woven fabric or unwoven fabriccomposed of one, two or more members, for example synthetic fibers suchas polyamides, polyesters, polyacrylonitrile, polyvinyl chloride,polyolefins, polyamino acids and glass fibers, regenerated fibers suchas viscose fiber, acetate fiber and the like, natural fibers such ascotton, silk, wool, linen and collagen obtained by fraying naturalleathers, or a sheet-like material constituted by one, two or moremembers, for example, synthetic resins such as polyamides, polyesters,polyacrylonitrile, polyvinyl chloride, polyolefins and polyamino acids,natural leathers from which silver surfaces have been removed, collagenobtained from waste leathers, natural rubber and synthetic rubber. Asthe organic solvent, there may be used conventional solvents, e.g.,halogenated hydrocarbons, alkyl esters of alkanoic acid, dimethylsulfoxide, dimethyl formamide and the like, which are capable ofdissolving polyglutamic acid-'y-esters. As the polyglutamicacid-'y-esters, there may be used those of the poly-L-glutamic acidseries or the poly-D-glutamic acid series or a mixture of such polymers.Although the homoor copolymers or blend polymers (polyamides) of anykind of glutamic acid-'y-esters as given in the following formula withor without other amino acid or acids or derivatives thereof:

cook m 7' c oo Y o OOH including those which are either optically activeor optically inactive can be used as the film or adherent according tothe present invention, it is more desirable to use the homoor copolymersor blend polymers of glutamic acid-y-ester of 'y-esters having X or Ygroup selected from the following residue with or without other aminoacid or acids: a monoor di-valent hydrocarbon residue consisting of asaturated or unsaturated aliphatic hydrocarbon residue having one tocarbons, a saturated or unsaturated cycloaliphatic hydrocarbon residuehaving four to 20 carbons, an aromatic hydrocarbon residue having six to20 carbons including aryl, arylene, alkaryl, alkarylene, aralkyl,aralkenyl, aralkylene, and aralkenylene type, and a residue belonging inthe above-mentioned types of hydrocarbon having a substituent orsubstituents selected from the group consisting of chloro, bromo,fluoro, nitro, cyano (nitrile), alkoxy, carboalkoxy, carboaryloxy,carboalkaryloxy, carboaralkoxy, monoand di-alkylated amino, acylatedamino, carboalkoxyamino, and carboaralkoxyamino.

Typical of ester groups represented by X are the same as those for Rdescribed later, and those for Y are ethylene, propylene, ,butylene,trimethylene, tetramethylene, pentamethylene, hexamethylene, 2-butenylene, cyclopentylene, cyclohexylene, cyclohexenylene, p-phenylene,and residues derived from pdi(hydroxymethyl)-benzene,p-di(hydroxymethyl)- cyclohexane, diethylene glycol, dipropylene glycol.

Typical examples of polymers are: homopolymer such aspoly-'y-methyl-glutamate, poly-'y-ethyl-glutamate,poly-7%i-propyl)-glutamate, poly-y-(n-propyU- glutamate,poly-y-(n-butyl)-glutamate, poly-y-(t, secor i-butyl)-glutamate,poly-y-benzyl-glutamate, polyamide polymer of 0 O -di(y-glutamyl)ethylene glycol and polyamide polymer of 0, 0 -di('y-glutamyl)trimethylene glycol; copolymer such as copoly-ymethyl glutamate-y-ethylglutamate, copoly-y-methyl glutamate-'y-(n-propyl)-glutamate,copoly-y-methyl glutamate-'y-(i-propyl) glutamate, copoly-y-methylglutamate-'y-(n-butyl) glutamate, copoly-y-methylglutamate-'y-benzyl-glutarnate, copoly-y-methyl glutamatealanine,copoly-y-methyl glutamate-Ne-acetyl-lysine, copoly-y-methyglutamate-methionine, copoly-ymethyl glutamate-y-ethylglutamate-'y-(n-propyl) glutamate, copoly-y-methyl glutamate-'y-ethylglutamatey-(i-propyl) glutamate, copoly-y-methyl glutamate- 0 ,0'y-glutamyl) ethylene glycol-'y-(i-propyl) glutamate, copoly-y-methylglutamate-'y-ethyl glutamate-ybutyl glutamate, and copoly-y-methylglutamatealanine-methionine, blend polymer such as blend polymer ofpoly-'y-methyl glutamate and poly-'y-ethyl glutamate, of poly-'y-methylglutamate and poly-'y-(npropyl)-glutamate, of poly-'y-methyl glutamateand p0ly-y-(i-propyl)-glutamate, of poly-'y-methyl glutamate andpoly-'y-(n-butyl)-glutamate, of poly-y-methyl glutamate, poly-'y-ethylglutamate and poly-'y-(n-butyl)-glutamate, of poly-'y-methyl glutamateand poly-ybenzyl glutamate, of poly-'y-methyl glutamate and polyalanine,of poly-'y-methyl glutamate, poly-'y-ethyl glutamate and polyalanine, ofpoly-'y-methyl glutamate and poly-Ne-acetyllysine, of poly-'y-methylglutamate and polymethionine, of poly-'y-methyl glutamate, polyalanineand polymethionine, of poly-y-ethyl glutamate and poly-'y-(n-butyl)glutamate, of poly-y-ethyl glutamate and poly-y-(n-propyl)-glutamate, ofpoly-'yethyl glutamate and poly-'y-(i-propyl)-glutamate, ofpoly-'y-ethyl glutamate and polyalanine, of poly-'y-ethyl glutamate andpoly-Ne-acetyl'lysine, of poly-y-ethyl glutamate and polymethionine, ofpoly-'y-methyl glutamate, polyamide polymer of 0,0 -di(y-glutamyl)ethylene glycol and polyalanine, of poly-'y-methyl glutamate, polyamidepolymer of 0,0 -di('y-glutamyl) trimethylene glycol and polyy-butylglutamate, and blend polymer of poly-'y-rnethyl glutamate, polyalanineand polymethionine.

The acidic amino acid derivatives to be used in the process of thepresent invention are compounds represented by the general formulas:

000m 0061i} 5mg R3 looms,

I N H2)n CH-Rq {h OORz, (lHzln (ilQORs COOR COOR COOR i COR: COR: COOR:H -N H-C-N H-C-N i J) I H2) H-Rt (CH2)n OOR ($112) JOOR5 OOR COORr COOK;COOR i COOR: CO L CO HC--N H-CN Rg N Ru H CO 1 CO CHR ((3112)., HR; (CZHUn JOORs ((5111),,

0H, ,n (CHDm or o=i )coom 0L looon,

N N JJOR: 3300B: (10) wherein, R and R are the same or different est'erresidue selected from the group consisting of a saturated or unsaturatedaliphatic hydrocarbon residue having one to 20 carbons, a saturated orunsaturated cycloaliphatic hydrocarbon residue having four to 20carbons, an aromatic hydrocarbon residue including aryl, alkaryl andaralkyl type having six to 20 carbons, and a residue belonging in theabove-mentioned types of hydrocarbon residue having a substituent orsubstituents selected from the group consisting of chloro, bromo,fluoro, nitro, cyano(nitrile), alkoxy, carboalkoxy, carboaryloxy,carboalkaryloxy, carboaralkoxy, monoand di-alkylated amino, acylatedamino, carboalkoxyamino, and carboaralkoxyamino; R, and R are the sameor different and respectively represent a hydrogen or a hydrocarbonresidue selected from the group consisting of a saturated or unsaturatedaliphatic hydrocarbon residue having one to 20 carbons, a saturated orunsaturated cycloaliphatic hydrocarbon residue having four to 20carbons, an aromatic hydrocarbon residue including aryl, alkaryl andaralkyl type having six to 20 carbons, and a residue belonging to theabove-mentioned types of hydrocarbon residue having a substituent orsubstituents selected from the group consisting of chloro, bromo,fluoro, nitro, cyano(nitrile), hydroxy, alkoxy, carboxy, carboalkoxy,carboaryloxy, carboaralkoxy, carboalkaryloxy, arylazo, alkarylazo(including alkoxyarylazo), sulfo (80 B), monoor di-alkylated amino,acylated amino, carboalkoxyamino, and carboaralkoxyamino; R representsan OH, an alkoxy, or a aliphatic hydrocarbon residue selected from thegroup consisting of a saturated or unsaturated aliphatic hydrocarbonresidue having one to six carbons, and the said residue having asubstituent or substituents selected from chloro, bromo, fluoro, nitro,cyano (nitrile), alkoxy, carboalkoxy, carboaryloxy, carboalkaryloxy,carboaralkoxy, amino, monoor dialkylated amino, acylated amino,carboalkoxyamino, and carboaralkoxyamino; R. represents a divalenthydrocarbon residue selected from the group consisting of a saturated orunsaturated aliphatic hydrocarbon residue having two to 20 carbons, asaturated or un saturated cycloaliphatic hydrocarbon residue having fourto 14 carbons, an aromatic hydrocarbon residue including arylene,alkarylene and aralltylene type having six to 20 carbons, and a residuebelonging to the above-mentioned type of hydrocarbon residue having asubstituent or substituents selected frog the group consisting ofchloro, bromo, fluoro, nitro, cyano (nitrile), alkoxy, monoanddi-alkylated amino, acylated amino, carboalkoxyamino,carboaralkoxyamino, arylazo, alkarylazo (including alkoxyarylazo),carboalkoxy, carboaryloxy, carboalkaryloxy and carboaralkxoy;

m is an integer from 1 to 18; and

n is an integer from 0 to 30.

Typical substituents of the ester of N-substituted or N,N-disubstitutedcompounds of the aforesaid acidic amino acid are formyl, acetyl,propionyl, butyryl, valeryl, dodecanoyl (lauroyl), palmitoyl, stearoyl,benzoyl, phenylacetyl, carbobenzoxy (benzyloxy-carbonyl), chloroacetyl,dichloroacetyl, mono-, di-, or tribromoacetyl, trichloroacetyl, mono-,dior trifluoroacetyl, carbocyclohexyloxy (cyclohexyloxycarbonyl),carbocyclopentyloxy (cyclopentyloxycarbonyl), carbo-tert-butyloxy(tert-butyloxycarbonyl), tert-amyloxycarbonyl, tolyloxycarbonyl,allyloxycarbonyl, 'y-chlorobutyryl, p-chlorocarbobenzyoxy,pbromocarbobenzoxy, p-methoxycarbobenzoxy,p-(pmethoxyphenylazo)-carbobenzoxy, p-nitrocarbobenzoxy,p-cyanocarbobenzoxy, o-carbomethoxybenzoyl, o-carboethoxybenzoyl,phthaloyl, succinyl, fumaroyl, maleoyl, citraconoyl, itaconoyl,crotonoyl, vinylacetyl, oleoyl, glutaryl, muconoyl,a,a'-dimethylmuconoyl, methyl, ethyl, n-propyl and isomers thereof,n-butyl and isomers thereof, n-pentyl and isomers thereof; n-hexyl andisomers thereof, n-octyl and isomers thereof, ndecyl and isomersthereof, ndodecyl and isomers thereof, n-hexadecyl (cetyl), stearyl,oleyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl,cyclobutyl methyl, cyclopentylmethyl, cyclohexylmethyl, phenyl, benzyl,o-tolyl, B- phenylethyl, p-tolylmethyl, p-chlorobenzyl, pnitrobenzyl,p-cyanobenzyl, p-methoxybenzyl, p-ethoxybenzyl, pentachloroobenzyl,p-chlorophenyl, pentachlorophenyl, p-nitrophenyl o-(2-chlorotolyl),methoxymethyl, ethoxymethyl, 2-hydroxyethyl, 2- nitroethyl,2-cyanoethyl, Z-methoxyethyl, 2- bromoethyl, 1,2-dichloropropyl,2,3-dichloropropyl, 2- chloropropyl, 2-chloroethyl, vinyl, crotyl, andallyl.

Typical groups of the ester group represented by the R, and R are:methyl, ethyl, n-propyl, i-propyl, n-butyl and isomers thereof, n-pentyland isomers thereof, nhexyl and isomers thereof, n-heptyl and isomersthereof, n-octyl and isomers thereof, n-decyl and isomers thereof,n-dodecyl (lauryl) and isomers thereof, cetyl, stearyl, oleyl,cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl,cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyclooctylmethyl,methylcyclohexyl, phenyl, o-tolyl, p-tolyl, benzyl, B-phenylethyl,p-tolylmethyl, o-tolylmethyl, o- (2-chlorotolyl), methoxymethyl,ethoxymethyl, 2- nitroethyl, 2-chloroethyl, 2-bromoethyl, 2-fluoroethyl,Z-cyanoethyl, 2-chloropropyl, 3-chloropropyl, 1,2- dichloropropyl,2,3-dichloropropyl, 3-bromopropyl, vinyl, allyl, crotyl, p-chlorobenzyl,p-bromobenzyl, pfluorobenzyl, p-nitrobenzyl, p-cyanobenzyl,p-methoxybenzyl, o-carboethyoxybenzyl, p-carboethoxybenzyl,p-carbomethoxybenzyl, pentachlorobenzyl, o-methoxybenzyl,p-ethoxybenzyl, p-methoxyphenyl, pchlorophenyl, p-nitrophenyl,pentachlorophenyl, pcarbomethoxy-phenyl, p-(N-methylaminophenyl), p-(N-ethylaminophenyl), p-(N,N-dimethylaminophenyl),p-(N,N-diethylaminophenyl), p-N-methyl-N- ethylaminophenyl),p-(N-methylaminobenzyl), p-(N- ethylaminobenzyl),p-(N,N-dimethylaminobenzyl), p- (N,N-diethylaminobenzyl), p-(N-methyl-N-ethylaminobenzyl), p-(N-acetylaminophenyl), p-(N- acetyl-aminobenzyl),p-(N-carbomethoxyaminophenyl), p-(N-carbomethoxyamino-benzyl), B-(dimethylaminoethyl), B-(carboethoxyethyl), and p-(N-carbobenzoxyaminophenyl), Z-methoxyethyl, 2- ethoxyethyl,3-methoxypropyl, 3-ethoxypropyl, 3-butoxypropyl, 4-methoxybutyl,4-ethoxybutyl, and 2-butoxyethyl.

Representative compounds to be used include diesters and mixed esters ofacidic amino acids, B-substituted acidic amino acids, N-substitutedacidic amino acids, N,N-disubstituted acidic amino acids, fl-substitutedN-substituted acidic amino acids and B-substituted N,N-disubstitutedacidic amino acids wherein the said acidic amino acids are such as, forexample, aminomalonic acid, asparatic acid, glutamic acid, aaminoadipicacid, a-aminopimelic acid, a-aminosuberic acid, a-aminosebacic acid,2-pyrrolidone-5-carboxylic acid, 2-piperidone-6-carboyxlic acid and thelike, the substituents on the B-position are hydroxy, methoxy, ethoxy,n-propoxy, n-butoxy, i-propoxy, i-butoxy, sec-butoxy, tert-butoxy,methyl, ethyl, n-propyl, ipropyl, n-butyl, i-butyl, sec-butyl, t-butyl,bromoand chloromethyl, bromoand chloroethyl, bromoand chloromethoxy aridbromo and chloroethoxy, the substituents on bromo- N-position areformyl, acetyl, propionyl, butyryl, valeryl, dodecanoyl (lauroyl),palmitoyl, stearoyl, benzoyl, phenylacetyl, carbobenzoxy(benzyloxycarbonyl), chloroacetyl, dichloroacetyl, trichloroacetyl,mono-, dior tri-bromoacetyl, mono-, dior trifluoroacetyl,carbocyclohexyloxy (cyclohexyloxycarbonyl), carbocyclopentyloxy(cyclopentyloxyacarbonyl), carbo-tert-butyloxy (tert-butyloxycarbonyl),tert-amyloxycarbonyl, tolytloxycarbonyl, allyloxycarbonyl,y-chlorobutyryl, p-chlorocarbobenzoxy, pbromocarbobenzoxy,p-methoxycarbobenzoxy, p-(p'- methoxyphenylazo)-carbobenzoxy,p-nitrocarbobenzoxy, p-cyanocarbobenzoxy, o-carbo-methoxybenzoyl,o-carboethoxybenzoyl, phthaloyl, succinyl, fumaroyl, maleoyl,citraconoyl, itaconoyl, crotonoyl, vinylacetyl, oleoyl, glutaryl,muconoyl, a,a-dimethylmuconoyl, methyl, ethyl, n-propyl and isomersthereof, n-butyl and isomers thereof, n-pentyl and isomers thereof,n-hexyl and isomers thereof, n-octyl and isomers thereof, n-decyl andisomers thereof, ndodecyl and isomers thereof, hexadecyl (cetyl),stearyl, oleyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl,

cyclooctyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl,phenyl, benzyl, o-tolyl, B-phenylethyl, p-tolylmethyl, p-chlorobenzyl,p-nitrobenzyl, p-cyanobenzyl, p-methoxybenzyl, p-ethoxybenzyl,pentachlorobenzyl, p-chlorphenyl, pentachlorophenyl, pnitrophenyl,o-(2-chlorotolyl), methoxymethyl, ethoxymethyl, Z-hydroxyethyl,2-nitroethyl, 2-cyannoethyl, 2methoxyethyl 2-bromoethyl,1,2-dichloropropyl, 2,3- dichloropropyl, 2-chloropropyl, 3-chloropropyl,2- chloroethyl, vinyl, crotyl, and allyl and the ester groups aremethyl, ethyl, n-propyl, i-propyl, n-butyl and isomers thereof, n-pentyland isomers thereof, n-hexyl and isomers thereof, n-heptyl and isomersthereof, noctyl and isomers thereof, n-decyl and isomers thereof,n-dodecyl (lauryl) and isomers thereof, cetyl, stearyl, oleyl,cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl,cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyclooctylmethyl,methylycyclohexyl, phenyl, o-tolyl, p-tolyl, benzyl, B-phenylethyl,ptolylmethyl, o-tolylmethyl, o-(2-chlorotolyl), methoxymethyl,ethoxymethyl, 2-nitroethyl, 2-chloroethyl, 2- bromoethyl, 2-fluoroethyl,2-cyanoethyl, 2-chloropropyl, 3-chloropropyl, 1,2-dichloropropyl, 2,3-dichloropropyl, 3-bromopropyl, vinyl, allyl, crotyl, pchlorobenzyl,p-bromobenzyl, p-fluorobenzyl, pnitrobenzyl, p-cyanobenzyl,p-methoxybenzyl, o-carboethoxybenzyl, p-carboethoxybenzyl,p-carbomethoxybenzyl, pentachlorobenzyl, o-methoxybenzyl,p-ethoxybenzyl, p-methoxyphenyl, pchlorophenyl, p-nitrophenyl,pentachlorophenyl, pcarbomethoxy-phenyl, p-(N-methylaminophenyl), p-(N-ethylaminophenyl), p-(N,N-diethylaminophenyl),p-(N-methyl-N-ethylaminophenyl), p-(N-methylaminobenzyl),p-(N-ethylaminobenzyl), p-(N,N- dimethylaminobenzyl),p-(N,N-diethylaminobenzyl), p-(N-methyl-N-ethylaminobenzyl), p-(N-acetylaminophenyl), p-(N-acetylaminobenzyl), p-(N-carbomethoxy-aminpphenyl), p-(N-carbomethoxyaminobenzyl),fi-(dimethylamino)ethyl, B(carboethoxy)ethyl, and p-(N-carbobenzoxyaminophenyl), 2-methoxy-ethyl, 2-ethoxyethyl,3-methoxypropyl, 3- ethoxypropyl, 3-butoxypropyl, 4-methoxybutyl, 4-ethoxybutyl and 2-butoxyethyl. These derivatives to be used may beeither optically active or inactive.

The following examples are given as merely being illustrative of thepresent invention, and accordingly, should not be considered aslimiting.

EXAMPLE 1 A viscous liquid obtained by thoroughly kneading a mixturecomprising 92 parts of poly-y-methyl-L-glutamate (molecular weight:about 400,000), 8 parts of dibutyl glutamate ester and 900 parts of 1,2-dichloroethane is coated so as to form a layer of 0.3 mm in thickness ona polyester fiber substrate cloth of 0.5 mm in thickness. The coatedproduct is then heated at 50 60C to evaporate the solvent, therebyproducing a sheet-like article. The thus obtained sheet-like articlevery closely resembles natural leather in both tensile strengthandelongation and looks more like natural leather in all aspects such asfeeling, touching and other characteristics, than that obtained by usingpoly-ymethyl-L-glutamate alone. Intrinsic volume resistivity of thesheet-like article thus obtained is measured to slow less than l0"/Q.cm(voltage: V).

9 EXAMPLE 2 Properties of the film prepared from a material obtained bythoroughly kneading an ethane dichloride solution ofpoly-y-methyl-L-glutamate (molecular weight: about 350,000) with dibutylglutamate ester in an amount of 52 percent based on the content of thepolymer are as shown in Table 2. The sheet-like article prepared byformation of this film on the substrate cloth had properties veryclosely resembling those of natural leather. That is, its tensilestrength is almost equal to that of the silver surface of naturalleather, that is about 120 180 kg/cm, and its elongation is found to beabout 90 120 percent, which is almost the same as that of naturalleather. The feeling and other characteristics of the sheet-like productthus obtained are very similar to those of natural leather.

EXAMPLE 3 A film prepared by kneading an ethane dichloride solution ofpoly-y-methyl-glutamate (molecular weight: about 350,000) with dibutylaspartate ester in an amount of 0 52 percent based on the content of thepolymer showed almost the same result as in the film in Example 2wherein the dibutyl glutamate ester is used. A sheet-like articleprepared by formation of this film on the substrate cloth showed feelingand other characteristics closely resembling those of natural leather inlike manner as in the case of Example 1.

EXAMPLE 4 An unwoven fabric substrate consisting of 50 percent of cottonand 50 percent of rayon staple is coated with a polyurethane typeadhesive so as to form a layer having about 0.02 mm. thickness thereon.When the coated layer is semi-dried, a mixture obtained by thoroughlykneading together 90 parts of poly-'y-butyl- L-glutamate (molecularweight: about 300,000), 10 parts ofN,N-dimethylglutamate-di-(2-ethylhexyl) ester and 900 parts of ethanetetrachloride is coated thereon so as to form a layer of about 0.2 mm inthickness. The coating is then dried to obtain a synthetic leatherresembling natural leather in both tensile strength and elongation.

EXAMPLE 5 90 Parts of p0ly-y-benzyl-D-glutamate (molecular weight: about400,000), 10 parts of benzyl aminomalonate and 1000 parts of dioxane arethoroughly kneaded together. The resultant mixture is coated in 0.3 mmthickness on a poly-'y-methyl-glutamate fiber substrate cloth on thesurface of which a polyurethane type adhesive is previously coated. The

resultant coated product is dried to obtain a synthetic leather havingproperties very closely resembling those of natural leather.

EXAMPLE 6 A synthetic leather prepared by the same procedure as in thecase of Example 1, using a mixture comprising 92 parts ofpoly-y-methyl-L-glutamate (molecular weight: about 300,000), 8 parts ofdibutyl N-acetylglutamate and 900 parts of 1,2-dichloroethane, showedfeeling, touching and other characteristics closely resembling those ofnatural leather in like manner as in the case of Example 1.

EXAMPLE 7 A film prepared by the same-procedure as in the case ofExample 2, using a mixture comprising poly-ymethyl-L-glutamate(molecular weight: about 400,000) and dibutyl N-acetylglutamate inamount of 0 to 52 percent based on the content of the polymer showedalmost the same result as in he film in Example 2. A synthetic leatherprepared by the same procedure as in the case of example 2 showedfeeling, touching and other characteristics closely resembling those ofnatural leather.

EXAMPLE 8- A synthetic leather prepared by the same procedure as in thecase of Example 1, using a mixture of parts ofpoly-'y-methyl-D-glutamate (molecular weight: about 350,000), 10 partsof dibutyl N-acetylaspartate and 900 parts of 1,2-dichloroethane, showedfeeling, touching and other characteristics closely resembling those ofnatural leather in like manner as in the case of Example 1.

EXAMPLE 9 A synthetic leather prepared by the same procedure as insynthetic the case of Example 4, using a mixture of 90 parts ofpoly-y-(n-butyl)-L-glutamate (molecular weight: about 250,000), 10 partsof dibutyl N-phenylacetylglutamate and 900 parts of l,2-dichloroethane,showed feeling, touching and other characteristics closely resemblingthose of natural leather in like manner as in the case of Example 1.

EXAMPLE 10 A synthetic leather prepared by the same procedure as in thecase of Example 5, using a mixture of 90 parts of y-benzyl-D-glutamate(molecular weight: about 450,000), 10 parts ofN-chloroacetylaminomalonate and 900 parts of dioxane, showed the sameresult as in that of Example 5.

EXAMPLE 1 l A synthetic leather prepared by the same procedure as in thecase of Example 1, using a mixture comprising 90 parts of copolymer(molecular weight: about 200,000) of 'y-methyl-L-glutamate and'y-(n-butyD-L- glutamate (7:3), 10 parts ofdi-(i-propyl)-N-acetylglutamate and 900 parts of 1,2-dichloroethane,showed the same result as in that of Example 1.

EXAMPLE 12 A synthetic leather prepared by the same procedure as in thecase of Example 1, using a mixture comprising 92 parts of copolymer(molecular weight: about 250,000) of 'y-methyl-D-glutamate,'y-methoxyethyl-D- glutamate and N-acetyl-L-lysine (8:221), 8 parts ofdi- (chloroethyl) N-acetylglutamate and 900 parts of tetrachloroethane,showed the same result as in that of Example 1.

EXAMPLE 13 A synthetic leather prepared by the same proceudre as in thecase of Example 4, using a mixture of 90 parts of copolymer (molecularweight: about 250,000) of yethyl-L-glutamate, 'y-(n-propyU-L-glutamateand L- alanine (8: l :1 10 parts of di-(n-propyl) N- acetylaminoadipateand 900 parts of 1,2-

dichloroethane, showed the same result as in that of Example 4.

EXAMPLE 14 A synthetic leather prepared by the same procedure as in thecase of Example 1, using a mixture of 92 parts of blend polymer ofpoly-y-methyLL-glutamate (molecular weight: about 400,000) andpoly-y-(t-butyl)-L-glutamate (molecular weight: about 200,000) (8:2), 8parts of y-methyl-y-butyl N-acetyl-glutamate and 900 parts of1,2-dichloroethane, showed the same result as in that of Example 1.

EXAMPLE 15 A synthetic leather prepared by the same procedure as in thecase of Example 4, using a mixture of 90 parts of blend polymer ofpoly-'y-methyl-L-glutamate (molecular weight: about 200,000),poly-L-alanine (molecular weight: 350,000) andpoly-'y-benzyl-L-glutamate (molecular weight: 450,000) (921:1), 10 partsof dibenzyl a-N-acetylamino B-acetoxyadipate and 900 parts of1,2-dichloro-ethane and dioxane (1:1), showed the same result as in thatof Example 4.

EXAMPLE 16 A synthetic leather prepared by the same procedure as in inthe case of Example 4, using a mixture of 90 parts of blend polymer ofpoly-'y-ethyl-D-glutamate (molecular weight: about 300,000) andpolyamine polymer of ',0 -di('y-glutamyl) ethylene glycol (molecularweight: about 250,000), parts of di(cyclohexyl)N-acetyl-B-methylglutamate and 900 parts of l,2-dichloroethane, showedthe same results as in that of Example 4.

The invention being thus described, it will be obvious that the same maybe varied in many ways. Such variations are not to be regarded as adeparture from the spirit and scope of the invention, and all suchmodifications are intended to be included within the scope of thefollowing claims.

What is claimedis:

l. A composite comprising a substrate coated with a film comprising anadmixture consisting of (1) a major amount of a polymer selected fromthe group consisting of (i) homopolymer of glutamic acid 'y-ester, (ii)copolymer of glutamic acid 'y-ester with one or two members selectedfrom other glutamic acid y-esters and alanine, lysine, methionine andtheir derivatives and (iii) blend polymer of glutamic acid-ester polymerand other one or two polymers selected from other glutamic acid y-esterpolymers and polymers of alanine, lysine, methionine and theirderivatives, the glutamic acid y-ester in above (i), (ii) and (iii)being selected from the optically active or inactive group given in thefollowing formulas: I

wherein X is selected from the monovalent hydrocarbon groups consistingof a saturated or unsaturated aliphatic hydrocarbon residue having oneto 20 carbons, a saturated or unsaturated cycloaliphatic hydrocarbonresidue having four to 20 carbons, aromatic hydrocarbon residue havingsix to 20 carbons including aryl, alkaryl, aralkyl and aralkenyl type,and a residue belonging in the above-mentioned types of hydrocarbonhaving a substituent or substituents selected from the group consistingof chloro, bromo, fluoro, nitro, cyano, alkoxy, carboalkoxy,carboaryloxy, carboalkaryloxy, carboaralkoxy, monoand di-alkylatedamino, acylated amino, carboalkoxyamino and carboaralkoxyamino, and Y isselected from the divalent hydrocarbon group consisting of a saturatedor unsaturated aliphatic hydrocarbon residue having one to 20 carbons, asaturated or unsaturated cycloaliphatic hydrocarbon residue having fourto 20 carbons, an aromatic hydrocarbon residue having six to 20 carbonsincluding arylene, alkarylene, aralkylene and aralkenylene type, and aresidue belonging to the above-mentioned types of hydrocarbon having asubstituent or substituents selected from the group consisting ofchloro, bromo, fluoro, nitro cyano, alkoxy, carboalkoxy, carboaryloxy,carboalkaryloxy, carboaralkoxy, monoand di-alkylated amino, acylatedamino, carboalkoxyamino, and carboaralkoxyamino; and (2) a minor amountof an acidic amino acid derivative or mixture thereof represented by thegeneral formulas:

000R; 000R (CHM;

R2 R; i OJ; i ooon R3 \R; N In)" 0114:.

boon,

000B, coon, coon, l COR: Com 000R: II- N H- -N/ H-C-N H H \H H011 I l- 42) doom Hz) doom OOR5 600R, COOR1 000R! oooR, co co HC--N/ HCN/ Rfi-C--N/ I oo i oo CHR, ormn um, (5H2), (300R5 Cn 00R, room (CH2)m (CH2)mO1 0 j coonl o= J-COOR1 N N 00R, boom wherein, R and R are the same ordifferent ester residue selected from the group consisting of asaturated or unsaturated aliphatic hydrocarbon residue having one to 20carbons, a saturated or unsaturated cycloaliphatic hydrocarbon residuehaving four to 20 carbons, an aromatic hydrocarbon residue includingaryl, alkaryl, and aralkyl type having six to 20 carbons, and a residuebelonging to the above-mentioned types of hydrocarbon residue having asubstituent or substituents selected from the group consisting ofchloro, bromo, fluoro, nitro, cyano, alkoxy, carboalkoxy, carboaryloxy,carboalkaryloxy, carboaralkoxy, monoand di-alkylated amino, acylatedamino, residue carboalkoxyamino carboaralkoxyamino; R and R are the sameor different and respectively represent a hydrogen or a hydrocarbonresidue selected from the group consisting of a saturated or unsaturatedaliphatic hydrocarbon residue having one to 20 carbons, a saturated orunsaturated cycloaliphatic hydrocarbon residue having four to 20carbons, an aromatic hydrocarbon residue including aryl, alkaryl, andaralkyl type having six to 20 carbons, and a residue cyano, to theabove-mentioned types of hydrocarbon residue having a substituent orsubstituents selected from the group consisting of chloro, bromo,fluoro, nitro, cyano, hydroxy, alkoxy, carboxy, carboalkoxy,carboaryloxy, carboaralkoxy, carboalkaryloxy, arylazo, alkarylazo,sulfo, monoor di-alkylated amino, acylated amino, carboalkoxyamino andcarboaralkoxyamino; R, represents an 01-1, an alkoxy, or a aliphatichydrocarbon residue selected from the group consisting of a saturated orunsaturated aliphatic hydrocarbon residue having one to six carbons, andthe said residue having the substituent or substituents selected fromchloro, bromo, fluoro, nitro, cyano, alkoxy, carboalkoxy, carboaryloxy,carboalkaryloxy, carboaralkoxy, amino, monoor di-alkylated amino,acylated amino, carboalkoxyamino, and carboaralkoxyamino; R represents adivalent hydrocarbon residue selected from the group consisting of asaturated or unsaturated aliphatic hydrocarbon residue having two to 20carbons, a saturated or unsaturated cycloaliphatic hydrocarbon residuehaving four to 14 carbons, an aromatic hydrocarbon residue includingarylene, alkarylene and aralkylene type having six to 20 carbons and aresidue belonging to the above-mentioned types of hydrocarbon residuehaving a substituent or substituents selected from the group consistingof chloro, bromo, fluoro, nitro, cyano, alkoxy, monoand di-alkylatedamino, acylated amino, carboalkoxyamino, carboaralkoxyamino, arylazo,alkarylazo, carboalkoxy, carboaryloxy, carboalkaryloxy, andcarboaralkoxy; m is a number from 1 to 18; and n is a number from 0 to30.

2. The composite of claim 1, wherein a polyurethane an adhesive isinterposed between the substrate and the film.

3. The composite of claim 1, wherein the substrate is a woven fabricmade from fibers selected from the group consisting of polyamide fibers,polyester fibers, polyacrylonitrile fibers, polyvinyl chloride fibers,polyolefin fibers, polyamino acid fibers, glass fibers, viscose fibers,regenerated acetate fibers, cotton fibers, silk fibers, wool fibers,linen fibers and collagen fibers.

4. The composite of claim 1, wherein the substrate is a sheet selectedfrom the group consisting of polyamides, polyesters, polyacrylonitrile,polyvinyl chloride, polyolefins, polyamino acids, natural leathers,collagen, and natural and synthetic rubbers.

5. The composite of claim 1, wherein X is selected form the groupconsisting of methyl, ethyl, n-propyl, ipropyl, n-butyl and isomersthereof, n-pentyl ad isomers thereof, n-hexyl and isomers thereof,n-heptyl and isomers thereof, n-octyl and isomers thereof, n-

decyl and isomers thereof, n-dodecyl and isomers thereof, cetyl,stearyl, oleyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl,cyclooctyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexymethyl,cyclooctylmethyl, methylcyclohexy, phenyl, Otolyl, p-tolyl, benzyl,B-phenylethyl, p-tolylmethyl, o-tolylmethyl, o- 2-chlorotolyl,methoxymethyl, ethoxymethyl, 2- nitroethyl, 2-chloroethyl, 2-bromoethyl,2-fluoroethyl, 2-cyanoethyl, 2-chloropropyl, -3-chloropropyl,dichloropropyl, 2,3-dich1oropropyl, 3-bromopropyl, vinyl, allyl, crotyl,p-chlorobenzyl, p-bromobenzyl, pfluorobenzyl, p-nitrobenzyl,p-cyanobenzyl, p-methoxybenzyl, ocarboethoxybenzyl, p-carboethoxybenzyl,oand p-carbomethoxybenzyl, pentachlorobenzyl omethoxybenzyl,p-ethoxybenzyl, p-methoxyphenyl, pethoxyphenyl, p-chlorophenyl,p-nitrophenyl, pentachlorophenyl, p-carbomethoxyphenyl, p-N-methylaminophenyl, p-N-ethylaminophenyl, p-N,N- dimethylaminophenyl,p-N,N-diethyl-aminophenyl, p- N,N-dimethylaminobenzyl,p-N,N-diethylaminobenzyl, p-N-methyl-N-ethylaminobenzyl, p-N-methylaminobenzyl, p-N-acetylaminophenyl, p-N- acetylaminobenzyl,p-N-carbomethoxyaminophenyl, p- N-carbomethoxyamino-benzyl,B-dimethy1aminoethyl, B-carboethoxyethyl, p-N-carbobenzoxyaminopheny1,Z-methoxyphenyl, 2-ethoxyethyl, 3-methoxypropyl, 3- ethoxypropyl,3-butoxypropyl, 4-rnethoxybutyl, 4- ethoxybutyl and 2-butoxyethyl, and Yis selected from the group consisting of ethylene, propylene,trimethylene, tetramethylene, pentamethylene, hexamethylene,2-butenylene, cyclopentylene, cyclohexenylene, cyclohexylene,p-phenylene and residues derived from p-di(hydroxymethylbenzene, p-di-(hydroxy-methyl) cyclohexane, diethylene glycol and dipropylene glycol.

6. The composite of claim 1, wherein the acidic amino acid derivative isa member selected from the group consisting of the diesters and mixedesters of amino acids, B-substituted amino acids, N-substituted aminoacids, N,N-disubstituted amino acids, B-substituted N-substituted aminoacids and B-substituted N,N-disubstituted amino acids wherein the saidamino acid is selected from the group consisting of aminomalonic acid,aspartic acid, glutamic acid, aaminoadipic acid, a-aminopimeric acid,a-aminosuberic acid, and a-aminosebacic acid; the substituent orsubstituents on the B-position are selected from the group consisting ofhydroxy, methoxy, ethoxy, npropoxy, n-butoxy, i-propoxy, i-butoxy,sec-butoxy, tert-butoxy, methyl, ethyl, n-propyl, i-propyl, n-butyl,ibutyl, butyl and t-butyl; the substituent or substituents on the Nposition are selected from the group consisting of formyl, acetyl,propionyl, butyryl, valeryl, lauroyl, palmitoyl, stearoyl, benzoyl,phenylactyl, carbobenzoxy, chloroacetyl, dichloroacetyl,trichloroacetyl, mono-bromoacetyl, carbocyclohex' yloxy,carbo-tert-butyloxy, vinylacetyl, oleoyl, glutaryl, muconoyl, a,a'-dimethylmuconoyl, methyl, ethyl, npropyl and isomers thereof, n-butyland isomers thereof, n-pentyl and isomers thereof, n-hexyl and isomersthereof, n-octyl and isomers thereof, n-decyl and isomers thereof,n-dodcyl and isomers thereof, cetyl, stearyl, oleyl, cyclobutyl,cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclobutylmethyl,cyclopentylmethyl, cyclohexylmethyl, phenyl, benzyl,

different member selected from the group consisting of methyl, ethyl,n-propyl, i-propyl, n-butyl, and isomers thereof, n-pentyl and isomerthereof, nhexyl and isomers thereof, n-heptyl and isomers thereof,cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, phenyl,o-tolyl, p-tolyl, benzyl, B-phenylethyl, p-tolylmethyl, o-tolylmethyl,o-(2-chlorotolyl), methoxymethyl, ethoxymethyl, 2-chloroethyl,2-bromoethyl, 2-chloropropyl and 3-chloropropyl.

1. A composite comprising a substrate coated with a film comprising anadmixture consisting of (1) a major amount of a polymer selected fromthe group consisting of (i) homopolymer of glutamic acid gamma -ester,(ii) copolymer of glutamic acid gamma -ester with one or two membersselected from other glutamic acid gamma -esters and alanine, lysine,methionine and their derivatives and (iii) blend polymer of glutamicacid-ester polymer and other one or two polymers selected from otherglutamic acid gamma -ester polymers and polymers of alanine, lysine,methionine and their derivatives, the glutamic acid gamma -ester inabove (i), (ii) and (iii) being selected from the optically active orinactive group given in the following formulas: wherein X is selectedfrom the monovalent hydrocarbon groups consisting of a saturated orunsaturated aliphatic hydrocarbon residue having one to 20 carbons, asaturated or unsaturated cycloaliphatic hydrocarbon residue having fourto 20 carbons, aromatic hydrocarbon residue having six to 20 carbonsincluding aryl, alkaryl, aralkyl and aralkenyl type, and a residuebelonging in the above-mentioned types of hydrocarbon having asubstituent or substituents selected from the group consisting ofchloro, bromo, fluoro, nitro, cyano, alkoxy, carboalkoxy, carboaryloxy,carboalkaryloxy, carboaralkoxy, mono- and di-alkylated amino, acylatedamino, carboalkoxyamino and carboaralkoxyamino, and Y is selected fromthe divalent hydrocarbon group consisting of a saturated or unsaturatedaliphatic hydrocarbon residue having one to 20 carbons, a saturated orunsaturated cycloaliphatic hydrocarbon residue having four to 20carbons, an aromatic hydrocarbon residue having six to 20 carbonsincluding arylene, alkarylene, aralkylene and aralkenylene type, and aresidue belonging to the above-mentioned types of hydrocarbon having asubstituent or substituents selected from the group consisting ofchloro, bromo, fluoro, nitro cyano, alkoxy, carboalkoxy, carboaryloxy,carboalkaryloxy, carboaralkoxy, mono- and di-alkylated amino, acylatedamino, carboalkoxyamino, and carboaralkoxyamino; and (2) a minor amountof an acidic amino acid derivative or mixture thereof represented by thegeneral formulas:
 2. The composite of claim 1, wherein a polyurethane anadhesive is interposed between the substrate and the film.
 3. Thecomposite of claim 1, wherein the substrate is a woven fabric made fromfibers selected from the group consisting of polyamide fibers, polyesterfibers, polyacrylonitrile fibers, polyvinyl chloride fibers, polyolefinfibers, polyamino acid fibers, glass fibers, viscose fibers, regeneratedacetate fibers, cotton fibers, silk fibers, wool fibers, linen fibersand collagen fibers.
 4. The composite of claim 1, wherein the substrateis a sheet selected from the group consisting of polyamides, polyesters,polyacrylonitrile, polyvinyl chloride, polyolefins, polyamino acids,natural leathers, collagen, and natural and synthetic rubbers.
 5. Thecomposite of claim 1, wherein X is selected form the group consisting ofmethyl, ethyl, n-propyl, i-propyl, n-butyl and isomers thereof, n-pentylad isomers thereof, n-hexyl and isomers thereof, n-heptyl and isomersthereof, n-octyl and isomers thereof, n-decyl and isomers thereof,n-dodecyl and isomers thereof, cetyl, stearyl, oleyl, cyclobutyl,cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclobutylmethyl,cyclopentylmethyl, cyclohexymethyl, cyclooctylmethyl, methylcyclohexy,phenyl, 0tolyl, p-tolyl, benzyl, Beta -phenylethyl, p-tolylmethyl,o-tolylmethyl, o-2-chlorotolyl, methoxymethyl, ethoxymethyl,2-nitroethyl, 2-chloroethyl, 2-bromoethyl, 2-fluoroethyl, 2-cyanoethyl,2-chloropropyl, 3-chloropropyl, 1,2-dichloropropyl, 2,3-dichloropropyl,3-bromopropyl, vinyl, allyl, crotyl, p-chlorobenzyl, p-bromobenzyl,p-fluorobenzyl, p-nitrobenzyl, p-cyanobenzyl, p-methoxybenzyl,o-carboethoxybenzyl, p-carboethoxybenzyl, o- and p-carbomethoxybenzyl,pentachlorobenzyl o-methoxybenzyl, p-ethoxybenzyl, p-methoxyphenyl,p-ethoxyphenyl, p-chlorophenyl, p-nitrophenyl, pentachlorophenyl,p-carbomethoxyphenyl, p-N-methylaminophenyl, p-N-ethylaminophenyl,p-N,N-dimethylaminophenyl, p-N,N-diethyl-aminophenyl,p-N,N-dimethylaminobenzyl, p-N,N-diethylaminobenzyl,p-N-methyl-N-ethylaminobenzyl, p-N-methylaminobenzyl,p-N-acetylaminophenyl, p-N-acetylaminobenzyl,p-N-carbomethoxyaminophenyl, p-N-carbomethoxyamino-benzyl, Beta-dimethylaminoethyl, Beta -carboethoxyethyl,p-N-carbobenzoxyaminophenyl, 2-methoxyphenyl, 2-ethoxyethyl,3-methoxypropyl, 3-ethoxypropyl, 3-butoxypropyl, 4-methoxybutyl,4-ethoxybutyl and 2-butoxyethyl, and Y is selected from the groupconsisting of ethylene, propylene, trimethylene, tetramethylene,pentamethylene, hexamethylene, 2-butenylene, cyclopentylene,cyclohexenylene, cyclohexylene, p-phenylene and residues derived fromp-di(hydroxymethylbenzene, p-di-(hydroxy-methyl) cyclohexane, diethyleneglycol and dipropylene glycol.